Butadiene extraction



Patented June 7, 1949 BUTADIENE EXTRAGTION lohn;` B; Lovell, Baton Rouge, La., assignor to.

Standard` OilY Development Company, aI corporation of, Delawar AT ENT OFFICE Application March 29, 1946, SeriaPNo. 658i208`i (Cl: 26a-6.815)- 3 Claims.

This 4invention relates to improvements in' the extraction andconcentration of diolensg and relates'partic-ularly to improvementsiin the extraction andconcentration of diolens where an ammoniacal cuprous acetate solution is used` asl the extraction agent.

Ammoniacall cuprous salt solutions, such as those of cuprous nitrate, salicylate, cresolate, phenolataiormate, carbonate, acetate, chloride, etc., have beenused for the separation of` unsatu urated hydrocarbons from mixtures-.off saturated and unsaturated hydrocarbons, such as: clef-lus from para'ns and also for the separation of diolens from olefns. For example, a solution containing@ to 'rnols of cuprouscopper., 10.5 to 12;mols of ammonia and 4 mols offacetic acid', and having av pH value of 19.5 to 12.5, hasl been used extensively for concentrating diolens, for example, butadiene, from mixtures of both lsr/,tturated and'unsaturated hydrocarbons.

Thel mixture of hydrocarbons obtained by cracking petroleum oils contains together with the olens, dioleins such as butadiene-and' also small but-varying amounts of acetylenic materialsl having the followingy boiling points:

Methyl acetylene 9.18 Butadienev 24.0'6 Vinyl acetylene 41.0 Ethyl; acetylene; 47,7' Dimethyl acetylene 80.4

The composition of theV mixture oi hydrocarest; those; obtained by catalytic dehydrogena--- tion'of-butenes are higher, and those obtained by cracking at hightemperatures are generally the highest. Where extremely high temperatures', ranging; from: 1.406o to 1801.1o F.; were used in cracking, the: acetyleniccontentincreased up to` 5% by weight of. the,v mix-tureof` hydrocarbons having-thefsame number of carbonA atoms to the molecule.y

The lower acetylenic compounds; such,v as methylacetylene, can be separatedby distillation fmmthefraction containing four carbon'. atoms to,

2 the molecule; Dimethyl acetylene boi-ling;l aty a higher temperature'can also be separated by disev tillation. Vinyl acetyleneeand ethylacetylenaare not readily' separated by. distillationbu-tarefab sorbed by; ammoniacal cuprous.- acetate@ solution.` which, at thesame time, absorbsff the butadiene.- Theepresencevof acetylenic compoundsiin abuta diene-extract is-,undesirablel and varirnismeth-t` ods have been; devisedv for the separatom oilacetylene and butadiene as: they:- are" recovered;- from. the ammoniacal cuprous acetate; solution., Thelone method: generally used is, that oft poly-'1 merization; that is, byfincreasing` thev temperature, the -acetylenic ycompoundsftend-to -polymerizeor,Y toundergootherreactions such ascopolymerizaftion withthe -dio1efins present, hydration; and/or; othenreact-ions.whichl are not clearly` identified. and hence are 'classed for convenience f as u polfy--A merization" reactions,- ther products beingzsirnilarly classed: asspolymers. @neidiicultyencountered' inusing this` method. ot `polymerization is: that theSproducts-vary considerably, i; e.,somefo'r`.` thefpolymersfare--llquid somefplasticonsemie-solid. someare soluble inhydrocarbon,solvents and may b ereadily: removed by the usc-of suclrA solvents; on: the :other hand, somel are insolublel in; hydro-,-y carbon solvents and.' are generally remoyed by: filtration.4 Some; of the polymerizedacetylenes are also foundfto be readilynsolubleiinwater andi.-

therefore,.as the ammoniacalcuprous acetate so-. lution is an. aqueous copper solution, the acetylenic` polymers are not readilyy extracted by the use ofi these solvents and they are, likewise, not readily removabley by ordinary filtration. The exact composition of these acetylenic polymer products that are solublein water'is not: known;

though they are known to contain oxygen.. andf nitrogen, together with carbon and`hydrogen.-,

Considerable diiiiculty has beenexperiencedin the operation, especiallyof a liquid phaseL buta# diene extraction unit, where theseacetylenic poly.-

mer products are formed, as they, are: surface` active materials which tend to promotefoamingf of the solution when contacted with,v a gas'v and:

emulsion formation. whenI the solution is con-f tacted with-a liquid hydrocarbon. Themam diri culty encountered is severe solution, foaming if.

theconcentration, of these acetylenic polymer products is allowed-:to build-up impartoi` thesplant.

Funthen, it, has been; found. that foaming con.4 ditions are aggravated by the presence oiflnelyfdivided@ solid. particles'y which emulsifywith the solutionito formfvery,stableremulsionswhihicani;

be broken most easily by the application of heat. It has been found that these finely divided particles of rust, polymer, or any foreign material that is present, are concentrated by surface tension action at points in the extraction units where there exists a liquid-liquid interface. It is found that, after periods of smooth operation, the concentration of foam and emulsion producing material at the interface is such that any upset in flow tends to dislodge the material, resulting in severe solution foaming and emulsions. This foaming and emulsion reduces the stage eiciency of both the absorption and rejection sections and quite often results in severe solution spilling from the desorber.

According to this invention, the foamants and emulsiers are prevented from concentrating by withdrawing the material from the liquid-liquid interfaces to a drum equipped with a steam heating coil. In the drum the material is submitted to temperatures high enough to desorb any hydrocarbons and to polymerize any foam producing compounds to higher molecular weight, innocuous polymers. The solution is then circulated through a lter press to remove solids and heavy polymers present and then is returned to the system. Polymer oils are separated by skimming or extraction with light hydrocarbons, such as liquid butene before or after heating. These extracts of polymer oils are suitable for use as drying oils with or without further modification. The molecular weight of the extracted polymer oil may be regulated to give a product of the desired Viscosity by regulating the heating time and temperature. They may be further reacted with the dioleiins. The advantage of this invention is that the foam-producing polymers are subjected to heat, which further polymerizes them, in a separate system, thus preventing foaming in the stripper and towers.

Another advantage is that the solids are not allowed to concentrate at points in the system, thus reducing the danger of emulsication of the solution if foaming conditions do prevail.

Another advantage is that the solution containing foamants is desorbed in a closed system, eliminating the danger of solution spilling into water scrubbers, distillation equipment, etc., and loss of solution to the sewer.

'I'he concentrations of polymer and solid at a given withdrawal point are as follows:

P Wight er cnt Description of Sample Polymer Pr lcint Alcohol o s Extractable Lean Solution from Inventory 0, 04 0. 0l Absorption Settler Interface 0.10 0. 04 Rejection Sattler Interface 0.12 Absorbtion Settler Bottom.. 0.07 0. i Rejection Settler Bottom 0. 08 0. 03 Absorber Tower Interface 0.07 0.01 Composite of Emulsion Withdrawals.. 0.09 0.09 Lean Solution from Inventory 0. 04 0. 03 Absorber Tower Interface 0.06 0.01 Absorption Scttler Interface. 0.06 0. 04 Absorption Settler Bottom.. 0.05 0.20 Rejection Settlcr Interface... 0. 06 0. 03 Rejection Settler Bottom 0. 09 0. 03 Absorber Tower Interface 0.05 0.04 Composite of Emulsion Withdrawal (Before Desorption) 0.07 0. 04 Composite of Emulsion Withdrawal (After Desorption) 0.06 0. 29

The interface concentrations of these materials are greater than those found in the lean solutions.

The operation is illustrated with reference to the accompanying flow diagram, in which a crude liquid mixture of hydrocarbons containing the diolen to be extracted is represented as being introduced by feed line I into the absorber 3 for contact therein with the cuprous salt solution or solvent from line 2. The resulting extraction mixture is pumped from 3 through line 4 into settler 5 provided with baffle means 'I to reduce agitation of the liquids settling into two liquid phases having the liquid-liquid interface while foaming is prevented. The unabsorbed hydrocarbons of the upper liquid layer are withdrawn through line 6. The extract layer is withdrawn by line 3. The foam and emulsion producing material, which concentrates at the interface, is withdrawn therefrom at spaced points through manifold inlets of line 9 to a drum I D equipped with the steam heating coil II. The solution in which the foam producing compounds are polymerized is circulated from drum I0 to a filter press (not shown) by line I2, some of the solution requiring such further heat treatment being recycled from the filter press by line I3 to drum IIJ. Recovery is made of extracted hydrocarbons present in the solution containing the foam producing compound by desorption in drum I 0, the desorbed hydrocarbon vapor mixed with some water vapor being passed by line Ill through condenser I5 into separator I6, whence the hydrocarbon material is removed by line I'I and aqueous distillate is removed by line I3. The thus recovered hydrocarbon material and the resulting lean solution after filtration may be returned to the absorber 3.

I claim:

1. In a process for extracting a diolen from a mixture of hydrocarbons containing a diolenn with a cuprous salt solution, the steps which comprise contacting a liquid mixture of hydrocarbons containing the diolen with cuprous salt solution, passing the mixture of hydrocarbons and cuprous salt solution to a settler where separate layers of the mixture of hydrocarbons and the cuprous salt solution are formed and withdrawing from the interfaceI of the mixture of hydrocarbons and the cuprous salt solution a portion of said solution, thereby removing substances having a tendency to promote foaming and emulsication.

2. In a process for separating and concentrating butadiene from a mixture of hydrocarbons containing butadiene, the steps which comprise contacting a mixture of hydrocarbons containing butadiene in the liquid phase with an ammoniacal cuprous acetate solution, passing the mixture of hydrocarbons and cuprous salt solution to a settler where separate layers of the mixture of hydrocarbons and the cuprous salt solution are formed, removing a portion of the mixture of hydrocarbons and the ammoniacal cuprous acetate solution from the liquid-liquid interface, thereby removing substances having a tendency to promote foaming and emulsication, heating said mixture of hydrocarbons and ammoniacal cuprous acetate solution to polymerize any acetylenic compounds that may be present, separating the ammoniacal cuprous acetate solution and nltering to remove further any solids or semi-solids, and returning the purified solution to the ammoniacal cuprous acetate solution contacting the mixture of hydrocarbons.

3. In a process for separating and concentrating butadiene from a mixture of hydrocarbons containing butadiene, the steps which comprise contacting a mixture of hydrocarbons containing butadiene in the liquid phase with an am- REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date Staid et al. Mar. 6, 1945 Morrell et al Sept. 4, 1945 Arnold Feb. 26, 1946 Morrell et al May '1, 1946 

